The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxid...The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor（cmbsf） in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with depth.The relative high abundance and δ^34 S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone（SMTZ）.The sulfur isotopic composition of gypsum（from–25‰ to –20.7‰） is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great depths.The δ^34 S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.展开更多
Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life whic...Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life which is fueled by the hydrocarbons, the metabolic byproducts facilitate the precipitation of authigenic minerals. The study of methane seepage is also important to understand the oceanographic condition and local ecosystem. The seepage could be active or quiescent at different times. The geophysical surveys and the geochemical determinations reveal the existence of seepage. Among these methods, only geochemical determination could expose message of the dormant seepages. The active seepage demonstrates high porewater methane concentration with rapid SO42- depleted, low HaS and dissolved inorganic carbon （DIC）, higher rates of sulfate reduction （SR） and anaerobic oxidation of methane （AOM）. The quiescent seepage typically develops authigenic carbonates with specific biomarkers, with extremely depleted 13C in gas, DIC and carbonates and with enriched 34S sulfate and depleted 34S pyrite. The origin of methane, minerals precipitation, the scenario of seepage and the possible method of immigration could be determined by the integration of solutes concentration, mineral composition and isotopic fractionation of carbon, sulfur. Numerical models with the integrated results provide useful insight into the nature and intensity of methane seepage occurring in the sediment and paleo- oceanographic conditions. Unfortunately, the intensive investigation of a specific area with dormant seep is still limit. Most seepage and modeling studies are site-specific and little attempt has been made to extrapolate the results to larger scales. Further research is thus needed to foster our understanding of the methane seepage.展开更多
Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidi...Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidization of methane(AOM). Considering that the environmental conditions of the carbonates precipitation and the sources of carbon and organic matter need to be further declared, molecular fossils and compound-specific carbon isotopic investigations of the carbonates were conducted in this study. According to lipid biomarkers of 2,6,10,15,19-pentamethyleicosane(PMI) and squalane diagnostic to methanotrophic archaea, as well as the extremely low δ^(13)C values(as low as -1^(13).4‰) detected in samples JA-4, JA-5 and JX-8, these carbonates were revealed to be a result of AOM. Based on the varied δ^(13)C values of characteristic archaea biomarkers in specific samples, biogenic methane was proposed to be responsible for the formation of samples JA-4 and JA-5, whereas a mixed carbon source of ^(13)C-depleted methane and ^(13)C-enriched residual CO_2 from methanogenesis was suggested for the carbonate of JX-8 due to the co-occurrence of a highly positive δ^(13) C_(carb) value(+8‰) and a moderate ^(13)C depletion of PMI. The low content of AOM-related biomarkers and the absence of indicators for ANME-2 suggested that these carbonates were formed in weak seep settings. By comparison, no typical lipid biomarkers for methanotrophic archaea was detected in carbonate BG-12. The short-chain and long-chain n-alkanes accounted for 30% and 45% of all hydrocarbons, respectively, with a CPI value of 1.2, suggesting that the n-alkanes were derived from both marine organisms and terrestrial inputs. A low thermal maturity could be revealed by the incomplete equilibrium value of the C^(31)αβ 22S/(22S+22R) ratio(0.5), and the carbonate BG-12 was probably deposited in a suboxic condition indicated by a value of Pr/Ph ratio(2.5).展开更多
After the detection of the 1,20,21-C29 long-chain triol in some sediments and freshwater pteridophytes, in this study a new homologous long-chain triol, 1,3,4-C27-29, is detected for the first time in the Site4B core ...After the detection of the 1,20,21-C29 long-chain triol in some sediments and freshwater pteridophytes, in this study a new homologous long-chain triol, 1,3,4-C27-29, is detected for the first time in the Site4B core sediment in the northern South China Sea. The hydroxyl location and length of the carbon chain of this newly discovered triol differ from those of 1,20,21-C29 triol. The test results of its molecular distribution and individual carbon isotope reveal that 1,3,4-C29triol has a good correlation with n-C26-30 even carbon-numbered long-chain fatty alcohols, with R2 （n=68） values of 0.905, 0.929 and 0.903, respectively, and its carbon isotope composition, at -32.3%o_1.9%o, is similar to that of rt-C26.30, at -29.13%o^0.87%o, -32.98%o^1.28%o, and -32.98%o^1.28%o. 1,3,4-C29 triol from the Site4B core sediment and terrigenous long-chain fatty alcohol （n-C26.34） show highly consistent distribution trends in the entire section; thus, the former could serve as a proxy indicator of the terrigenous input. Considering that the 1,20,21-C29 triol in previous research belongs to Azolla, which are fresh water pteridophytes, the 1,3,4-C27-29 triol identified in this study might have similar biogenetic derivation. Thus, determination of its biogenic area and growing environment could provide potential organic geochemical evidence supporting the terrigenous input and source in the northern South China Sea.展开更多
This study investigated the composition of long-chain alkyl diols, triols, sec-alcohols, hydroxyl acids, and other hydroxylated compounds in Azolla imbricata and compared the organic alcohol components of Azolla filic...This study investigated the composition of long-chain alkyl diols, triols, sec-alcohols, hydroxyl acids, and other hydroxylated compounds in Azolla imbricata and compared the organic alcohol components of Azolla filiculoides, Azolla microphylla, and South China Sea （SCS） sediments in order to investigate the possible indication of Azolla being the biological source of diols and triols in SCS sediment. Large amounts of diols, monohydroxy acids, and sec-alcohols with internal hydroxy groups at ω20 were detected in the three types of Azolla. Among these, 1,ω20-diol and ω20-hydroxy acid exhibited strong even-odd predominance distribution, whereas co20-sec-alcohol exhibited strong odd-even predominance distribution. In addition, small amounts of diols, triols, and dihydroxy acids with internal hydroxy groups at 9, 10 or ω9, ω 10 were detected, among which the chain length of C29 was predominate. Compounds having similar structures as those in Azolla reflected a similar biosynthetic pathway： ω20-hydroxy acid exhibiting even-odd predominance distribution is decarboxylated to ω20-sec-alcohol exhibiting odd-even predominance distribution and converted to 1, ω20-diol with even-odd predominance distribution by acyl reduction; ω9,ω10-hydroxy acid is converted to 1,20,21（1, ω9, ω10）-triol by acyl reduction, and then converted to 9,10-diol by hydrogenation and dehydration. The alcohol components in A. imbricata were clearly not the biological source of 1,13/1,14/1,15-C28, 30, 32 diols and 1,3,4-C27.29 triols in the SCS sediment. Certain marine diatoms might be the source of 1,14-C28.30 diol in inshore sediment, but the biological source of diols and triols in the SCS sediment requires further investigation.展开更多
Here we reported the fatty-acids and their δ13 C values in seep carbonates collected from Green Canyon lease block 185 (GC 185;Sample GC-F) at upper continental slope (water depth:～540 m),and Alaminos Canyon lease b...Here we reported the fatty-acids and their δ13 C values in seep carbonates collected from Green Canyon lease block 185 (GC 185;Sample GC-F) at upper continental slope (water depth:～540 m),and Alaminos Canyon lease block 645 (GC 645;Sample AC-E) at lower continental slope (water depth:～2200 m) of the Gulf of Mexico.More than thirty kinds of fatty acids were detected in both samples.These fatty acids are maximized at C 16.There is a clear even-over-odd carbon number predominance in carbon number range.The fatty acids are mainly composed of n-fatty acids,iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso).The low δ13 C values (-39.99‰ to -32.36‰) of n-C 12:0,n-C 13:0,i-C 14:0 and n-C 14:0 suggest that they may relate to the chemosynthetic communities at seep sites.The unsaturated fatty acids n-C 18:2 and C 18:1 △9 have the same δ13 C values,they may originate from the Beggiatoa/Thioploca.Unlike other fatty acids,the terminally branched fatty acids (iso/anteiso) show lower δ13 C values (as low as -63.95‰) suggesting a possible relationship to sulfate reducing bacteria,which is common during anaerobic oxidation of methane at seep sites.展开更多
文摘异戊二烯类甘油二烷基甘油四醚脂类化合物(isoprenoid Glycerol dialkyl glycerol tetraethers,isoGDGTs)在海洋奇古菌(Thaumarchaeota)中广泛存在,其结构对温度变化的敏感性使其成为广受欢迎的古气候与古温度重建材料。在北冰洋和西太平洋气候以及黑潮等多种因素的影响下,冲绳海槽中部成为研究全新世以来古海洋和古气候变化的天然实验室。本文通过研究C14柱状沉积物的GDGTs组成、含量变化特征及其延伸的86个碳原子的四醚指标(tetraether index of tetraethers consisting of 86 carbons,TEX86H),分析冲绳海槽中部的GDGTs来源,并定量计算C14柱状沉积物记录的海洋表面温度(seasurfacetemperature,SST),从而探讨8.2ka以来冲绳海槽中部古温度变化的驱动机制。通过甲烷指数和支链/异戊二烯类指标等,我们确认isoGDGTs主要来自于氨氧化古菌,适用于古温度重建。距今8.2ka以来,TEX86H SST的变化范围是21.6~27.2℃。冲绳海槽中部SST主要受到西热带太平洋、低纬度冬季日晒量的影响;TEX86H指标记录的温度上升趋势与东亚夏季风强度的减弱不一致。7.4—6.6ka冷事件广泛存在于冲绳海槽的SST记录中,但只在TEX86H数据中显示较大幅度的降低(~5℃),我们推测可能受到Kikai-Akahoya火山灰(~7.3ka)的影响。
基金The Qingdao National Laboratory for Marine Science and Technology under contract No.QNLM2016ORP0210the National Natural Science Foundation of China under contract Nos 41306061,41473080 and 41376076the Scientific Cooperative Project by China National Petroleum Corporation and Chinese Academic of Sciences under contract No.2015A-4813
文摘The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor（cmbsf） in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with depth.The relative high abundance and δ^34 S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone（SMTZ）.The sulfur isotopic composition of gypsum（from–25‰ to –20.7‰） is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great depths.The δ^34 S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.
基金The National Natural Science Foundation of China under contract No.41376076the Natural Science Foundation of Guangdong Province under contract No.2015A030313718+1 种基金the Scientific Cooperative Project by China National Petroleum Corporation and Chinese Academy of Sciences under contract No.2015A-4813the National Marine Geological Project,China Geological Survey under contract No.GZH2012006003
文摘Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life which is fueled by the hydrocarbons, the metabolic byproducts facilitate the precipitation of authigenic minerals. The study of methane seepage is also important to understand the oceanographic condition and local ecosystem. The seepage could be active or quiescent at different times. The geophysical surveys and the geochemical determinations reveal the existence of seepage. Among these methods, only geochemical determination could expose message of the dormant seepages. The active seepage demonstrates high porewater methane concentration with rapid SO42- depleted, low HaS and dissolved inorganic carbon （DIC）, higher rates of sulfate reduction （SR） and anaerobic oxidation of methane （AOM）. The quiescent seepage typically develops authigenic carbonates with specific biomarkers, with extremely depleted 13C in gas, DIC and carbonates and with enriched 34S sulfate and depleted 34S pyrite. The origin of methane, minerals precipitation, the scenario of seepage and the possible method of immigration could be determined by the integration of solutes concentration, mineral composition and isotopic fractionation of carbon, sulfur. Numerical models with the integrated results provide useful insight into the nature and intensity of methane seepage occurring in the sediment and paleo- oceanographic conditions. Unfortunately, the intensive investigation of a specific area with dormant seep is still limit. Most seepage and modeling studies are site-specific and little attempt has been made to extrapolate the results to larger scales. Further research is thus needed to foster our understanding of the methane seepage.
基金supported by Qingdao National Laboratory for Marine Science and Technology(No.QNLM2016ORP0210)the NSF of China(No.41473080 and 41673029)
文摘Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidization of methane(AOM). Considering that the environmental conditions of the carbonates precipitation and the sources of carbon and organic matter need to be further declared, molecular fossils and compound-specific carbon isotopic investigations of the carbonates were conducted in this study. According to lipid biomarkers of 2,6,10,15,19-pentamethyleicosane(PMI) and squalane diagnostic to methanotrophic archaea, as well as the extremely low δ^(13)C values(as low as -1^(13).4‰) detected in samples JA-4, JA-5 and JX-8, these carbonates were revealed to be a result of AOM. Based on the varied δ^(13)C values of characteristic archaea biomarkers in specific samples, biogenic methane was proposed to be responsible for the formation of samples JA-4 and JA-5, whereas a mixed carbon source of ^(13)C-depleted methane and ^(13)C-enriched residual CO_2 from methanogenesis was suggested for the carbonate of JX-8 due to the co-occurrence of a highly positive δ^(13) C_(carb) value(+8‰) and a moderate ^(13)C depletion of PMI. The low content of AOM-related biomarkers and the absence of indicators for ANME-2 suggested that these carbonates were formed in weak seep settings. By comparison, no typical lipid biomarkers for methanotrophic archaea was detected in carbonate BG-12. The short-chain and long-chain n-alkanes accounted for 30% and 45% of all hydrocarbons, respectively, with a CPI value of 1.2, suggesting that the n-alkanes were derived from both marine organisms and terrestrial inputs. A low thermal maturity could be revealed by the incomplete equilibrium value of the C^(31)αβ 22S/(22S+22R) ratio(0.5), and the carbonate BG-12 was probably deposited in a suboxic condition indicated by a value of Pr/Ph ratio(2.5).
基金In addition,gratitude is expressed to the National Natural Science Foundation of China(Grant Nos.41303067,41103043&41273022)Funds of Chinese Academy of Sciences for Key Topics in Innovation Engineering(Grant No.KGZD-EW-301)+2 种基金State Key Laboratory of Organic Geochemistry Open Research Fund(Grant No.OGL-201209)CNPC-CAS Science and Technology Cooperation Project(Grant No.2015A-4813)the international partnership project team of Innovation of the Chinese Academy of Sciences for providing financial support
文摘After the detection of the 1,20,21-C29 long-chain triol in some sediments and freshwater pteridophytes, in this study a new homologous long-chain triol, 1,3,4-C27-29, is detected for the first time in the Site4B core sediment in the northern South China Sea. The hydroxyl location and length of the carbon chain of this newly discovered triol differ from those of 1,20,21-C29 triol. The test results of its molecular distribution and individual carbon isotope reveal that 1,3,4-C29triol has a good correlation with n-C26-30 even carbon-numbered long-chain fatty alcohols, with R2 （n=68） values of 0.905, 0.929 and 0.903, respectively, and its carbon isotope composition, at -32.3%o_1.9%o, is similar to that of rt-C26.30, at -29.13%o^0.87%o, -32.98%o^1.28%o, and -32.98%o^1.28%o. 1,3,4-C29 triol from the Site4B core sediment and terrigenous long-chain fatty alcohol （n-C26.34） show highly consistent distribution trends in the entire section; thus, the former could serve as a proxy indicator of the terrigenous input. Considering that the 1,20,21-C29 triol in previous research belongs to Azolla, which are fresh water pteridophytes, the 1,3,4-C27-29 triol identified in this study might have similar biogenetic derivation. Thus, determination of its biogenic area and growing environment could provide potential organic geochemical evidence supporting the terrigenous input and source in the northern South China Sea.
基金the National Natural Science Foundation of China(Grant Nos.41303067,41103043&41273022)the Chinese Academy of Sciences Knowledge Innovation Project(Grant No.KGZD-EW-301)the PetroChina-Chinese Academy of Sciences Science and Technology Cooperation Project(Grant No.2015A-4813)
文摘This study investigated the composition of long-chain alkyl diols, triols, sec-alcohols, hydroxyl acids, and other hydroxylated compounds in Azolla imbricata and compared the organic alcohol components of Azolla filiculoides, Azolla microphylla, and South China Sea （SCS） sediments in order to investigate the possible indication of Azolla being the biological source of diols and triols in SCS sediment. Large amounts of diols, monohydroxy acids, and sec-alcohols with internal hydroxy groups at ω20 were detected in the three types of Azolla. Among these, 1,ω20-diol and ω20-hydroxy acid exhibited strong even-odd predominance distribution, whereas co20-sec-alcohol exhibited strong odd-even predominance distribution. In addition, small amounts of diols, triols, and dihydroxy acids with internal hydroxy groups at 9, 10 or ω9, ω 10 were detected, among which the chain length of C29 was predominate. Compounds having similar structures as those in Azolla reflected a similar biosynthetic pathway： ω20-hydroxy acid exhibiting even-odd predominance distribution is decarboxylated to ω20-sec-alcohol exhibiting odd-even predominance distribution and converted to 1, ω20-diol with even-odd predominance distribution by acyl reduction; ω9,ω10-hydroxy acid is converted to 1,20,21（1, ω9, ω10）-triol by acyl reduction, and then converted to 9,10-diol by hydrogenation and dehydration. The alcohol components in A. imbricata were clearly not the biological source of 1,13/1,14/1,15-C28, 30, 32 diols and 1,3,4-C27.29 triols in the SCS sediment. Certain marine diatoms might be the source of 1,14-C28.30 diol in inshore sediment, but the biological source of diols and triols in the SCS sediment requires further investigation.
基金supported by the National Basic Research Program of China (Grant No.2009CB219508)National Natural Science Foundation of China (Grant Nos.40725011 and U0733003)+1 种基金the State Key Laboratory of Organic Geochemistry (Grant No.OGL-200811)Knowledge Innovation Program of Chinese Academy of Sciences (Grant No.KGCX2-YW-805)
文摘Here we reported the fatty-acids and their δ13 C values in seep carbonates collected from Green Canyon lease block 185 (GC 185;Sample GC-F) at upper continental slope (water depth:～540 m),and Alaminos Canyon lease block 645 (GC 645;Sample AC-E) at lower continental slope (water depth:～2200 m) of the Gulf of Mexico.More than thirty kinds of fatty acids were detected in both samples.These fatty acids are maximized at C 16.There is a clear even-over-odd carbon number predominance in carbon number range.The fatty acids are mainly composed of n-fatty acids,iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso).The low δ13 C values (-39.99‰ to -32.36‰) of n-C 12:0,n-C 13:0,i-C 14:0 and n-C 14:0 suggest that they may relate to the chemosynthetic communities at seep sites.The unsaturated fatty acids n-C 18:2 and C 18:1 △9 have the same δ13 C values,they may originate from the Beggiatoa/Thioploca.Unlike other fatty acids,the terminally branched fatty acids (iso/anteiso) show lower δ13 C values (as low as -63.95‰) suggesting a possible relationship to sulfate reducing bacteria,which is common during anaerobic oxidation of methane at seep sites.
